A Terminal Iron Nitrilimine Complex: Accessing the Terminal Nitride through Diazo N−N Bond Cleavage

A novel method for the N−N bond cleavage of trimethylsilyl diazomethane is reported for the synthesis of terminal nitride complexes. The lithium salt of trimethylsilyl diazomethane was used to generate a rare terminal nitrilimine transition metal complex with partially occupied d‐orbitals. This iron...

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Autores principales: Aghazada, Sadig, Miehlich, Matthias, Messelberger, Julian, Heinemann, Frank W., Munz, Dominik, Meyer, Karsten
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2019
Materias:
Communications
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6916540/
https://www.ncbi.nlm.nih.gov/pubmed/31529583
http://dx.doi.org/10.1002/anie.201910428
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author Aghazada, Sadig
Miehlich, Matthias
Messelberger, Julian
Heinemann, Frank W.
Munz, Dominik
Meyer, Karsten
author_facet Aghazada, Sadig
Miehlich, Matthias
Messelberger, Julian
Heinemann, Frank W.
Munz, Dominik
Meyer, Karsten
author_sort Aghazada, Sadig
collection PubMed
description A novel method for the N−N bond cleavage of trimethylsilyl diazomethane is reported for the synthesis of terminal nitride complexes. The lithium salt of trimethylsilyl diazomethane was used to generate a rare terminal nitrilimine transition metal complex with partially occupied d‐orbitals. This iron complex 2 was characterized by CHN combustion analysis, (1)H and (13)C NMR spectroscopic analysis, single‐crystal X‐ray crystallography, SQUID magnetometry, (57)Fe Mössbauer spectroscopy, and computational analysis. The combined results suggest a high‐spin d (6) (S=2) electronic configuration and an allenic structure of the nitrilimine ligand. Reduction of 2 results in release of the nitrilimine ligand and formation of the iron(I) complex 3, which was characterized by CHN combustion analysis, (1)H NMR spectroscopic analysis, and single‐crystal X‐ray crystallography. Treatment of 2 with fluoride salts quantitatively yields the diamagnetic Fe(IV) nitride complex 4, with concomitant formation of cyanide and trimethylsilyl fluoride through N−N bond cleavage.
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spelling pubmed-69165402019-12-23 A Terminal Iron Nitrilimine Complex: Accessing the Terminal Nitride through Diazo N−N Bond Cleavage Aghazada, Sadig Miehlich, Matthias Messelberger, Julian Heinemann, Frank W. Munz, Dominik Meyer, Karsten Angew Chem Int Ed Engl Communications A novel method for the N−N bond cleavage of trimethylsilyl diazomethane is reported for the synthesis of terminal nitride complexes. The lithium salt of trimethylsilyl diazomethane was used to generate a rare terminal nitrilimine transition metal complex with partially occupied d‐orbitals. This iron complex 2 was characterized by CHN combustion analysis, (1)H and (13)C NMR spectroscopic analysis, single‐crystal X‐ray crystallography, SQUID magnetometry, (57)Fe Mössbauer spectroscopy, and computational analysis. The combined results suggest a high‐spin d (6) (S=2) electronic configuration and an allenic structure of the nitrilimine ligand. Reduction of 2 results in release of the nitrilimine ligand and formation of the iron(I) complex 3, which was characterized by CHN combustion analysis, (1)H NMR spectroscopic analysis, and single‐crystal X‐ray crystallography. Treatment of 2 with fluoride salts quantitatively yields the diamagnetic Fe(IV) nitride complex 4, with concomitant formation of cyanide and trimethylsilyl fluoride through N−N bond cleavage. John Wiley and Sons Inc. 2019-10-31 2019-12-16 /pmc/articles/PMC6916540/ /pubmed/31529583 http://dx.doi.org/10.1002/anie.201910428 Text en © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the http://creativecommons.org/licenses/by/4.0/ License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
spellingShingle Communications
Aghazada, Sadig
Miehlich, Matthias
Messelberger, Julian
Heinemann, Frank W.
Munz, Dominik
Meyer, Karsten
A Terminal Iron Nitrilimine Complex: Accessing the Terminal Nitride through Diazo N−N Bond Cleavage
title A Terminal Iron Nitrilimine Complex: Accessing the Terminal Nitride through Diazo N−N Bond Cleavage
title_full A Terminal Iron Nitrilimine Complex: Accessing the Terminal Nitride through Diazo N−N Bond Cleavage
title_fullStr A Terminal Iron Nitrilimine Complex: Accessing the Terminal Nitride through Diazo N−N Bond Cleavage
title_full_unstemmed A Terminal Iron Nitrilimine Complex: Accessing the Terminal Nitride through Diazo N−N Bond Cleavage
title_short A Terminal Iron Nitrilimine Complex: Accessing the Terminal Nitride through Diazo N−N Bond Cleavage
title_sort terminal iron nitrilimine complex: accessing the terminal nitride through diazo n−n bond cleavage
topic Communications
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6916540/
https://www.ncbi.nlm.nih.gov/pubmed/31529583
http://dx.doi.org/10.1002/anie.201910428
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